EP0613924B1 - Methode zur Herstellung eines mit viskositätsstabilisierenden Verbindungen behandelten Naturkautschukes - Google Patents

Methode zur Herstellung eines mit viskositätsstabilisierenden Verbindungen behandelten Naturkautschukes Download PDF

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Publication number
EP0613924B1
EP0613924B1 EP94301165A EP94301165A EP0613924B1 EP 0613924 B1 EP0613924 B1 EP 0613924B1 EP 94301165 A EP94301165 A EP 94301165A EP 94301165 A EP94301165 A EP 94301165A EP 0613924 B1 EP0613924 B1 EP 0613924B1
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EP
European Patent Office
Prior art keywords
natural rubber
viscosity
rubber
hydrazide
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94301165A
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English (en)
French (fr)
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EP0613924A1 (de
Inventor
Hirotoshi Toratani
Eiji Nakamura
Hideki Aoyama
Yasushi Hirata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
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Bridgestone Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP4134493A external-priority patent/JPH06256570A/ja
Priority claimed from JP19251793A external-priority patent/JPH0748405A/ja
Priority claimed from JP19251693A external-priority patent/JPH0748404A/ja
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Publication of EP0613924A1 publication Critical patent/EP0613924A1/de
Application granted granted Critical
Publication of EP0613924B1 publication Critical patent/EP0613924B1/de
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides

Definitions

  • the present invention relates to a manufacturing method of natural rubber which imparts a good processability and excellent physical properties.
  • Natural rubber is produced in tropical countries such as the Kingdom of Thailand, Malaysia, and The republic of Indonesia. Natural rubber is used widely in the rubber industry, the tire industry and the like due to its excellent physical properties.
  • Mooney viscosity of the natural rubber is as low as 60 ⁇ 70.
  • the Mooney viscosity thereof increases up to nearly 90 ⁇ 100, that is gelation takes place ( so-called “storage hardening").
  • crosslinking is formed by the reaction of different kinds of bonds (an aldehyde group and the like ) in an isoprene chain with protein and amino acids in natural rubber and then gelation takes place (the mechanism has not been determined clearly yet in the literature).
  • the gelation in natural rubber (an increase in the amount of gel ) deteriorates processability.
  • natural rubber having a high molecular weight is preferable from a consideration of physical properties, and a decrease in molecular weight affects the physical properties of natural rubber.
  • Molecular weight and amount of gel are greatly influenced by rubber coagulation from natural rubber latex, storage of natural rubber and drying conditions after water-washing.
  • RSS ribbed smoked sheet
  • TSR Technical specified rubber
  • viscosity stabilizer for natural rubber
  • RRIM Rubber Research Institute of Malaysia
  • SMR-GP hydroxylamine sulfate
  • An object of the present invention is to solve the problem concerning drying conditions in the above-mentioned conventional manufacturing processes of natural rubber, that is to solve the problem concerning the drying conditions at the time of manufacturing RSS or TSR.
  • Another object of the present invention is to attempt the suppression of gelation and the prevention of a decrease in molecular weight.
  • Still another object is to provide a manufacturing method of natural rubber having both a good processability and excellent physical properties.
  • Yet another object of the present invention is to solve the above-mentioned problem that natural rubber having a high molecular weight and no foreign material cannot be obtained.
  • the present invention provides a manufacturing method of natural rubber which comprises the following consecutive steps:
  • the natural rubber is treated with a strainer after mixing with the viscosity stabilizer.
  • Drying temperature preferably ranges from 80 to 100°C.
  • the viscosity stabilizer comprises one or more hydrazide compounds of the following general formula, R-CONHNH 2 where R is selected from alkyl groups having 1 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms and aryl groups.
  • the content of the hydrazide compound(s) is preferably 0.001 part by weight or more based on 100 parts by weight of the natural rubber.
  • the drying is preferably conducted under conditions to result in 10% or less of the difference of gel content and 85% or more of molecular weight retention between before and after drying.
  • natural rubber containing viscosity stabilizers can be prepared by mixing viscosity stabilizers into dried natural rubber. It is necessary to add viscosity stabilizers to dried natural rubber as quickly as possible since gelation ( storage hardening ) proceeds even when the dried natural rubber is left at room temperature.
  • viscosity stabilizers used when natural rubber is prepared there may be used, for example, hydroxylamine sulfate, semicarbazide, dimedone(1,1-dimethylcyclohexane-3,5-dione) and hydrazide compounds (additives for natural rubber used in the present invention) of the following general formula (I), R-CONHNH 2 where R is selected from the group consisting of alkyl groups having 1 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms and aryl groups.
  • these viscosity stabilizers When these viscosity stabilizers are compounded into natural rubber, these viscosity stabilizers react with bonds of a different kind in an isoprene chain (such as an aldehyde group) resulting in blocking said bonds. Consequently, this reaction results in the prevention of the gelation reaction in natural rubber which causes the storage hardening and the suppression of an increase in the amount of gel.
  • bonds of a different kind in an isoprene chain such as an aldehyde group
  • Exemplary suitable hydrazide compounds having an alkyl group of 1 ⁇ 30 carbon atoms of the above-mentioned general formula (I) include: acethydrazide, hydrazide propionate, butylhydrazide, hydrazide laurate, hydrazide palmitate, hydrazide stearate and the like.
  • Exemplary suitable hydrazide compounds having a cycloalkyl group of 3 ⁇ 30 carbon atoms of the above-mentioned general formula (I) include: cyclopropyl hydrazide, cyclohexyl hydrazide, cycloheptyl hydrazide and the like.
  • a hydrazide compound having an aryl group of the above-mentioned general formula (I) may contain substituents, and examples of said compound include phenyl hydrazide (C 6 H 5 -CONHNH 2 ), o-, m-, p-tolyl hydrazide, p-methoxyphenyl hydrazide, 3,5-xylyl hydrazide, 1-naphthyl hydrazide and the like.
  • a fatty acid hydrazide having an alkyl chain is preferable.
  • viscosity stabilizers Although the above-mentioned hydroxylamine sulfate, semicarbazide and dimedone have been known as viscosity stabilizers, it has not previously been known to compound these viscosity stabilizers into natural rubber. For the first time, the present inventors have succeeded in developing the above-mentioned techniques. There can be attained for the first time prevention of a decrease in molecular weight and suppression of an increase in the amount of gel by employing viscosity stabilizers.
  • Hydrazide compounds of the above-mentioned general formula (I) are known materials, and manufacturing methods thereof are also known. However, it has not been known that the above-mentioned viscosity stabilizers of the present invention are compounded into natural rubber.
  • Hydrazide compounds of the above-mentioned general formula (I) are safe to handle. These compounds impart the effect of a constant viscosity when added to natural rubber, and the effect of a constant viscosity lasts for a long time.
  • these compounds may be added to natural rubber produced to prevent storage hardening, or these compounds may be added in the stage of mastication and the like.
  • the amount of the compound used as a viscosity stabilizer and selected from hydroxylamine sulfate, semicarbazide, dimedone or hydrazide compounds of the above-mentioned general formula (I) is preferably 0.001 part by weight or more based on 100 parts by weight of the natural rubber.
  • the amount of each viscosity stabilizer used is less than 0.001 part by weight based on 100 parts by weight of the natural rubber, the viscosity of natural rubber is not stabilized sufficiently.
  • the amount of viscosity stabilizers depends on a variety of natural rubbers used ( produced ) and a variety of viscosity stabilizers used, the amount preferably ranges from 0.01 to 3.0 parts by weight based on 100 parts by weight of natural rubber.
  • the amount thereof preferably ranges from 0.01 to 2.0 parts by weight based on 100 parts by weight of natural rubber.
  • each hydrazide compound when R has a carbon number from 1 to 5, the content of each hydrazide compound preferably ranges from 0.01 to 1.0 part by weight, more preferably 0.03 to 0.5 part by weight based on 100 parts by weight of natural rubber. In the case of acethydrazide having a carbon number of 1, the lower limit is preferably 0.04 part by weight or more.
  • the content of each hydrazide compound when R has a carbon number from 15 to 20, the content of each hydrazide compound preferably ranges from 0.1 to 3.0 parts by weight based on 100 parts by weight of natural rubber, more preferably from 0.1 to 0.5 parts by weight.
  • the lower limit is preferably 0.15 part by weight or more, and in the case of hydrazide stearate having a carbon number of 18, the lower limit is preferably 0.16 part by weight or more.
  • the hydrazide compounds of the above-mentioned general formula (I) may be contained individually or jointly in natural rubber in the range of above-mentioned content.
  • exemplary suitable hydrazide compounds of the above-mentioned general formula (I) above include acethydrazide, hydrazide propionate, butylhydrazide, hydrazide laurate, hydrazide palmitate, hydrazide stearate, cyclopropyl hydrazide, cyclohexyl hydrazide, phenyl hydrazide and the like.
  • an optional component such as softener, antioxidant and the like into natural rubber.
  • an optional component such as filler, reinforcer, softener, vulcanizer, vulcanization accelerator, vulcanization accelerator auxiliary, antioxidant and the like.
  • Natural rubber containing the above-mentioned viscosity stabilizers may be also treated under drying conditions to result in 10 % or less of the difference of gel content and 85 % or more of molecular weight retention, preferably 5 % or less of the difference of gel content and 90 % or more of molecular weight retention, between before and after drying.
  • drying conditions which keep the difference of gel content 10 % or less and the molecular weight retention 85 % or more vary depending upon the kind and the grade of natural rubber used (produced), it is preferable that drying temperature is set at 80 ⁇ 100 °C and drying time is as short as possible in order to prevent gelation and a decrease in molecular weight.
  • drying temperature is set at 80 ⁇ 100 °C.
  • gel formation rate becomes fast at less than 80 °C. Therefore, it is expected that this drying condition suppresses gelation and prevents a decrease in molecular weight of natural rubber.
  • natural rubber having a high molecular weight and no foreign material may be obtained by mixing viscosity stabilizers and the natural rubber with a mixer, an extruder and the like after conventional drying or treating under the above-mentioned drying conditions and by treating with a strainer thereafter.
  • Natural rubber having a high molecular weight and no foreign material obtained by the manufacturing method according to the present invention contains viscosity stabilizers and is treated with a strainer.
  • the object of strainer treatment is to remove foreign materials in natural rubber containing viscosity stabilizers.
  • foreign materials can be removed by passing natural rubber containing viscosity stabilizers through a mesh-like material formed at the point of an extruder.
  • a size of the mesh corresponding to 0.355mm (No.45) defined by ASTM E11 is preferable.
  • the size of the mesh may be changed suitably for natural rubber produced and the size of foreign materials contained in the natural rubber and the like.
  • a method for suppressing an increase in the viscosity of natural rubber which comprises adding to the natural rubber hydrazide compounds of the above-mentioned general formula (I).
  • the amount of the hydrazide compounds added is preferably 0.001 part by weight or more based on 100 parts by weight of natural rubber.
  • the amount of hydrazide compounds added is less than 0.001 part by weight, an increase in the viscosity of natural rubber may not be suppressed sufficiently.
  • the amount of hydrazide compounds added depends on natural rubber and hydrazide compounds. Preferably, the addition amount thereof ranges from 0.01 to 3.0 parts by weight based on 100 parts by weight of natural rubber.
  • the range of the addition amount of each hydrazide compound used for the method for suppressing an increase in the viscosity of natural rubber is the same as that of the content of hydrazide compounds used for natural rubber as a viscosity stabilizer.
  • Natural rubber was prepared by using an unsmoked sheet as raw rubber based on the drying conditions shown in the following Table 1.
  • the amount of gel, molecular weight, carbon black dispersibility and tensile strength of rubber vulcanized were determined by the following methods.
  • Dispersibility was determined using a microscope based on ASTM D2663B. The larger the value, the better the dispersibility.
  • Example 1 shows natural rubber treated under the drying conditions of the present invention and containing a viscosity stabilizer. Because of the viscosity stabilizer and the drying conditions of the present invention, an increase in the amount of gel was substantially low and the molecular weight was held substantially constant for 20 days after drying. Also, carbon black dispersibility and tensile strength of the natural rubber vulcanized were good even after leaving the natural rubber at 60 °C for 20 days.
  • Comparative Examples 1 and 2 are beyond the scope of the present invention and Comparative Example 1 is based on drying conditions of a conventional RSS, and Comparative Example 2 is based on drying conditions of a conventional TSR.
  • Natural rubber was prepared by using an unsmoked sheet as raw rubber based on the treatments shown in the following Table 2. The natural rubber was left at 60 °C for 20 days.
  • the amount of gel, molecular weight, carbon black dispersibility and tensile strength of rubber vulcanized were determined based on the above-mentioned methods (1) - (4).
  • the amount of foreign materials was determined based on the following method (5).
  • Examples 2 and 3 are within the scope of the present invention, and a viscosity stabilizer was contained in natural rubber, and a strainer treatment was carried out. According to Examples 2 and 3, even after leaving natural rubber for 20 days, an increase in the amount of gel and a decrease in molecular weight were suppressed, and the natural rubber is substantially free from foreign materials. Also, carbon black dispersibility and tensile strength of the rubber vulcanized were good.
  • Comparative Examples 3 ⁇ 5 are beyond the scope of the present invention.
  • a viscosity stabilizer was not contained and a strainer treatment was not carried out.
  • an increase in the amount of gel became remarkable, and the natural rubber contains large amount of foreign materials. Also, carbon black dispersibility and tensile strength of the rubber vulcanized became poor.
  • Comparative Example 4 a viscosity stabilizer was not contained, and a strainer treatment was carried out. Although the natural rubber is substantially free from foreign materials, an increase in the amount of gel became remarkable and carbon black dispersibility and tensile strength of rubber vulcanized became poor as well.
  • Comparative Example 5 a viscosity stabilizer was not contained, and a strainer treatment was carried out, and furthermore a mastication treatment was carried out. Although an increase in the amount of gel was suppressed, a decrease in molecular weight was remarkable, and tensile strength of the rubber vulcanized became poor.
  • Example Comparative Example 1 1 2 Drying conditions Drying time 2 hours 5 days 2 hours Drying temperature 100°C 60°C 120°C Viscosity stabilizer for natural rubber present absent absent Amount of gel Before drying 3% 3% 3% 20 days after drying 9% 27% 31% Difference of gel content + 6% + 24% + 28% Molecular weight Before drying 2.2 ⁇ 10 6 2.2 ⁇ 10 6 2.2 ⁇ 10 6 20 days after drying 1.9 ⁇ 10 6 2.0 ⁇ 10 6 1.5 ⁇ 10 6 Retention 86% 91% 68% After 20 days Carbon black dispersibility 89% 68% 64% Tensile strength(kg/cm 2 ) 301 284 276

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (5)

  1. Verfahren zum Herstellen von Naturkautschuk, umfassend die aufeinanderfolgenden Schritte:
    (1) Zapfen
    (2) Koagulation
    (3) Waschen mit Wasser
    (4) Entwässern
    (5) Trocknen
    (6) Mischen eines Viskositätsstabilisators mit dem getrockneten Naturkautschuk mit Hilfe eines Mischers und eines Extruders
    (7) Verpacken.
  2. Verfahren nach Anspruch 1, wobei der Naturkautschuk nach dem Mischen mit dem Viskositätsstabilisator mit einem Strainer behandelt wird.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Trocknungstemperatur im Bereich von 80° bis 100°C liegt.
  4. Verfahren nach Anspruch 1, 2 oder 3, wobei der Viskositätsstabilisator eine oder mehrere Hydrazid-Verbindungen der folgenden allgemeinen Formel umfasst: R-CONHNH2 worin R ausgewählt wird aus: Alkyl-Gruppen mit 1 bis 30 Kohlenstoffatomen, Cycloalkyl-Gruppen mit 3 bis 30 Kohlenstoffatomen und Aryl-Gruppen.
  5. Verfahren nach Anspruch 4, wobei der Gehalt an Hydrazid-Verbindung(en) bezogen auf 100 Gewichtsteile des Naturkautschuks 0,001 Gewichtsteile oder mehr beträgt.
EP94301165A 1993-03-02 1994-02-18 Methode zur Herstellung eines mit viskositätsstabilisierenden Verbindungen behandelten Naturkautschukes Expired - Lifetime EP0613924B1 (de)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP4134493 1993-03-02
JP4134493A JPH06256570A (ja) 1993-03-02 1993-03-02 天然ゴム用添加剤、その添加剤を含有したゴム組成物及びその添加剤による天然ゴムの粘度上昇抑制方法
JP41344/93 1993-03-02
JP192516/93 1993-08-03
JP19251793A JPH0748405A (ja) 1993-08-03 1993-08-03 天然ゴム及びその製造方法
JP192517/93 1993-08-03
JP19251793 1993-08-03
JP19251693 1993-08-03
JP19251693A JPH0748404A (ja) 1993-08-03 1993-08-03 天然ゴム及びその製造方法

Publications (2)

Publication Number Publication Date
EP0613924A1 EP0613924A1 (de) 1994-09-07
EP0613924B1 true EP0613924B1 (de) 2000-05-17

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EP94301165A Expired - Lifetime EP0613924B1 (de) 1993-03-02 1994-02-18 Methode zur Herstellung eines mit viskositätsstabilisierenden Verbindungen behandelten Naturkautschukes

Country Status (6)

Country Link
EP (1) EP0613924B1 (de)
CN (1) CN1084752C (de)
BR (1) BR9400783A (de)
DE (1) DE69424455T2 (de)
ES (1) ES2147769T3 (de)
MY (1) MY116207A (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5482597A (en) * 1994-11-23 1996-01-09 Basf Aktiengesellschaft Purification of crude (meth)acrylic acid
JPH10226734A (ja) 1996-12-09 1998-08-25 Bridgestone Corp 天然ゴム用恒粘度剤、恒粘度天然ゴム組成物及びその製造方法、並びに、天然ゴムの粘度上昇抑制方法
JP4111584B2 (ja) * 1998-04-13 2008-07-02 株式会社ブリヂストン 天然ゴムの製造方法
JP3698699B2 (ja) * 2000-11-07 2005-09-21 株式会社ブリヂストン ラテックスからの天然ゴム及びそれを含む組成物
US8389641B2 (en) * 2008-02-18 2013-03-05 Bridgestone Corporation Modified diene rubber, production method thereof, and rubber composition and tire using the rubber
CN103627044B (zh) * 2013-12-12 2015-06-24 西双版纳中化橡胶有限公司 一种恒粘天然橡胶及其制备方法
FR3034703B1 (fr) 2015-04-10 2017-03-24 Michelin & Cie Elimination de contaminants dans le caoutchouc naturel humide
EP3410519B1 (de) * 2016-01-29 2021-06-02 Zeon Corporation Binderzusammensetzung für wasserfreie sekundärbatterieelektroden, schlämmezusammensetzung für wasserfreie sekundärbatterieelektroden, elektrode für wasserfreie sekundärbatterien und wasserfreie sekundärbatterie
US11339272B2 (en) 2016-11-30 2022-05-24 Bridgestone Corporation Additive for rubber, rubber composition, and tire using the same
CN108424551B (zh) * 2018-03-30 2020-12-01 云南滇源橡胶有限公司 一种复合橡胶
CN111057275A (zh) * 2018-10-16 2020-04-24 上海中化科技有限公司 一种恒粘胶及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1472064A (en) * 1973-06-08 1977-04-27 Malaysia Rubber Res Inst Treatment of natural rubber

Also Published As

Publication number Publication date
BR9400783A (pt) 1994-11-01
EP0613924A1 (de) 1994-09-07
DE69424455T2 (de) 2001-01-18
DE69424455D1 (de) 2000-06-21
CN1084752C (zh) 2002-05-15
MY116207A (en) 2003-12-31
CN1095077A (zh) 1994-11-16
ES2147769T3 (es) 2000-10-01

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